Novel azole derivative and agricultural/horticultural fungicide containing said derivative as active ingredient

ABSTRACT

An azole derivative represented by the formula ##STR1## wherein X and Y independently represent a halogen atom, a phenyl group or a hydrogen atom, providing that at least one of X and Y is not a hydrogen atom, n represents an integer of 0, 1 or 2, and A represents a nitrogen atom or CH, and an agricultural/horticultural fungicide comprising the azole derivative as an active ingredient are disclosed. 
     The azole derivative exhibits an excellent effect in preventing and curing a wide spectrum of plant diseases and possesses low toxicity to mammals.

This is a division of application Ser. No. 07/443,582, filed Nov. 30,1989, now U.S. Pat. No. 4,962,278 which is a division of applicationSer. No. 07/129,629 filed Dec. 7, 1987, now U.S. Pat. No. 4,902,702.

BACKGROUND OF THE INVENTION

The present invention relates to an azole derivative useful as an activeingredient for preventing and curing plant diseases, a process for theproduction of the azole derivative, and an agricultural/horticulturalfungicide containing the azole derivative as an active ingredientthereof.

Numerous azole derivatives have been heretofore proposed for use as anactive ingredient of agricultural/ horticultural fungicides. The azolederivatives disclosed in Japanese Patent Application Laid-Open (KOKAI)No. 215,674 (1985) have an azolylmethyl group and a phenyl group bondedto the same carbon atom as shown by the following formula: ##STR2##wherein R₁ and R₂ independently represent a hydrogen atom, a hydroxylgroup or an alkyl group having 1 to 6 carbon atoms and X represents ahydrogen atom or a halogen atom.

Japanese Patent Application Laid-Open (KOKAI) No. 149,667 (1987)discloses compounds represented by the following formula: ##STR3##wherein Xs independently represent a halogen atom, an alkyl group, ahaloalkyl group, a phenyl group, a cyano group, or a nitro group, nrepresents an integer in the range of 0 to 5, and A represents anitrogen atom or CH.

The present inventors, with a view to developing anagricultural/horticultural fungicide possessing low toxicity to mammals,warranting safe handling, and exhibiting a highly satisfactory effect inpreventing and curing a wide spectrum of plant diseases, havesynthesized many azole derivatives and tested the practicability thereofas a fungicide. The present inventors have consequently found that theazole derivatives of a configuration having an azolylmethyl group and abenzyl group, a phenyl group, or a phenethyl group respectively bondedto adjacent carbon atoms in a cylcopentane ring are useful as an activeingredient of agricultural/horticultural fungicides possessing theaforementioned characteristics. The present invention has beenaccomplished based on this finding.

SUMMARY OF THE INVENTION

In a first aspect of the present invention, there is provided an azolederivative represented by the formula (I): ##STR4## wherein X and Yindependently represent a halogen atom, a phenyl group, or a hydrogenatom, providing that at least one of X and Y is not a hydrogen atom, nrepresents an integer of 0, 1 or 2, and A represents a nitrogen atom orCH.

In a second aspect of the present invention, there is provided a processfor the production of an azole derivative represented by the formula(I): ##STR5## wherein A, X, Y and n have the same meanings as definedabove, which comprises reacting a cyclopentanone derivative representedby the following formula (II): ##STR6## wherein A has the same meaningas defined above, with a Grignard reagent represented by the followingformula (III): ##STR7## wherein X, Y and n have the same meanings asdefined above and Z represents a halogen atom.

In a third aspect of the present invention, there is provided a processfor the production of an azole derivative represented by the followingformula (I): ##STR8## wherein A, X, Y and n have the same meanings asdefined above, which comprises hydrolyzing the ketal group in acyclopentanone derivative represented by the following formula (IV):##STR9## wherein A has the same meaning as defined above, therebyobtaining a cyclopentanone derivative represented by the followingformula (II): ##STR10## wherein A has the same meaning as defined above,and reacting said cyclopentanone derivative with a Grignard reagentrepresented by the following formula (III): ##STR11## wherein X, Y, Zand n have the same meanings as defined above.

In a fourth aspect of the present invention, there is provided acyclopentanone derivative represented by the following formula (II):##STR12## wherein A has the same meaning as defined above.

In a fifth aspect of the present invention, there is provided acyclopentanone derivative represented by the following formula (IV):##STR13## wherein A has the same meaning as defined above.

In a sixth aspect of the present invention, there is provided anagricultural/horticultural fungicide comprising as an active ingredienta fungicidally effective amount of an azole derivative represented bythe following formula (I): ##STR14## wherein A, X, Y and n have the samemeanings as defined above.

In a seventh aspect of the present invention, there is provided a methodfor preventing and curing plant deseases which comprises applying afungicidally effective amount of an azole derivative represented by thefollowing formula (I): ##STR15## wherein A, X, Y and n have the samemeanings as defined above, to plants.

BRIEF EXPLANATION OF THE DRAWINGS

FIG. 1 to FIG. 7 are infrared absorption spectra of the compounds No. 1to No. 7 according to the present invention listed in Table 1. FIG. 8and FIG. 9 are infrared absorption spectra of cyclopentanone derivativesrepresented by the formula (II) (FIG. 8 representing a compound having aCH group as the substituent A in the formula (II) and FIG. 9 a compoundhaving a N atom as the substituent A in the formula (II)). FIG. 10 andFIG. 11 are infrared absorption spectra of ketals of cyclopentanonederivatives represented by the formula (IV) (FIG. 10 representing acompound having a CH group as the substituent A in the formula (IV) andFIG. 11 a compound having a N atom as the substituent A in the formula(IV)).

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to an azole derivative useful as an activeingredient of an agricultural/horticultural fungicide, a process for theproduction of the azole derivative, and an agricultural/horticulturalfungicide comprising as an active component the aforementioned azolederivative, exhibiting a highly desirable effect in preventing andcuring a wide spectrum of plant diseases, possessing low toxicity tomammals, and excelling in safety of handling.

The azole derivatives of the present invention are represented by thefollowing formula (I): ##STR16## wherein X and Y independently representa halogen atom, a phenyl group or a hydrogen atom, providing that atleast one of X and Y is not a hydrogen atom, n represents an integer of0, 1 or 2, and A represents a nitrogen atom or CH.

The azole derivatives represented by the formula (I) are novel compoundsnot reported yet in literature. The melting points of examples of thecompounds according to the present invention are shown in Table 1.

                  TABLE 1                                                         ______________________________________                                        Compound                                                                              Meaning of symbol used in Formula (I)                                                                Melting                                        No.     X        Y        n     A      point (°C.)                     ______________________________________                                        1       4-Cl     H        0     N      Oily state                             2       4-Cl     H        1     N      127-130                                3       4-Cl     H        1     CH     152-153                                4       4-Cl     2-Cl     1     N      108-110                                5       4-Ph     H        1     N      153-154                                6       4-F      2-F      1     N      Oily state                             7       4-Cl     H        2     N      Oily state                             ______________________________________                                    

The infrared absorption spectra of the compounds cited exemplarily inTable 1 are shown in FIGS. 1 to 7 respectively.

The azole derivative according to the present invention is produced bythe following method.

The azole derivative represented by the formula (I) is obtained byreacting a cyclopentanone derivative represented by the followingformula (II): ##STR17## wherein A stands for a nitrogen atom or CH, witha Grignard reagent represented by the following formula (III): ##STR18##wherein X and Y independently represent a halogen atom, a phenyl groupor a hydrogen atom, providing that at least one of X and Y is not ahydrogen atom, n represents an integer of 0, 1 or 2, and Z represents ahalogen atom, in the presence of a diluent.

The cyclopentanone derivative of the formula (lI) which is used as thestarting material herein is a novel compound not reported yet inliterature and is obtained by reacting a known ketone represented by thefollowing formula (V): ##STR19## wherein R represents an eliminationgroup such as a halogen atom, a methanesulfonyloxy group and aparatoluenesulfonyloxy group (for example, the compound ##STR20## isdisclosed in Bull. Chem. Soc. Japan, 1975, Vol. 48, No. 9, 2579-2583),with 1,2,4-triazole or imidazole represented by the following formula(VI): ##STR21## wherein M represents a hydrogen atom or an alkali metaland A represents a nitrogen atom or CH, in the presence of a diluent.

The cyclopentanone derivative represented by the formula (II) can bealso obtained by hydrolyzing, under an acidic condition, a ketal ofcyclopentanone derivative represented by the following formula (IV):##STR22## wherein A represents a nitrogen atom or CH, which is obtainedby reacting a known ketal represented by the following formula (VII):##STR23## wherein R represents an elimination group such as a halogenatom, a methanesulfonyloxy group and a paratoluenesulfonyloxy group (forexample, the compound ##STR24## is disclosed in J. Chem. Soc. PerkinTrans. 1, 1978, No. 3, 209-214), with 1,2,4-triazole or imidazolerepresented by the aforementioned formula (VI) in the presence of adiluent.

As examples of the diluent which is used in the process for theproduction of the compound represented by the formula (I), there can becited ethers such as diethyl ether, diisopropyl ether andtetrahydrofuran and aromatic hydrocarbons containing ethers such asbenzene and toluene containing ethers. Among the diluents cited above,ethers are particularly preferable.

The process of production according to the present invention can beworked out, for example, by dissolving a Grignard reagent represented bythe formula (III) in a diluent described above and adding to theresultant solution a cyclopentanone derivative represented by theformula (II) preferably in an amount in the range of 0.3 to 1.0equivalent to the Grignard reagent, or conversely by dissolving thecyclopentanone derivative in the diluent and adding to the resultantsolution a solution of the Grignard reagent in the diluent.

Though the reaction can be carried out at any desired temperaturebetween the freezing point and the boiling point of the diluent used asa solvent, it is practically preferable to be carried out at atemperature in the range of 0° to 80° C. The reaction time is preferablyin the range of 0.5 to 3.0 hours. The reaction is preferably carried outunder stirring.

After the reaction described above is completed, the compoundrepresented by the formula (I) is obtained by pouring the reactionmixture resulting from the reaction into ice water, extracting theresultant mixture with an organic solvent such as ethyl acetate,chloroform and benzene, separating an organic layer from the mixture,washing the organic layer with water and drying the washed organiclayer, evaporating the dry organic layer under a reduced pressure, andpurifying the resultant residue. This purification can be effected bymeans of recrystallization or silica gel column chromatography, forexample.

As examples of the diluent which is used in producing the cyclopentanonederivative represented by the formula (II) from the compound of theformula (V) and the compound of the formula (VI), there can be citedhydrocarbons such as benzene, toluene, xylene and hexane; halogenatedhydrocarbons such as methylene chloride, chloroform and carbontetrachloride; ethers such as diethyl ether, diisopropyl ether andtetrahydrofuran; and acetonitrile, dimethyl formamide, and dimethylsulfoxide.

The production of the cyclopentanone derivative represented by theformula (II) is effected, for example, by dissolving a compoundrepresented by the formula (VI) in a diluent described above and addingto the resultant solution a compound represented by the formula (V),either directly or in a state dissolved in the diluent, preferably in anamount in the range of 0.3 to 1.0 equivalent to the compound of (VI), orconversely by dissolving the compound represented by the formula (V) inthe diluent and adding to the resultant solution a solution of thecompound represented by the formula (VI) in a diluent.

Though the reaction can be carried out at any desired temperaturebetween the freezing point and the boiling point of the diluent used asa solvent, it is practically preferable to be carried out at atemperature in the range of 0° to 80° C. The reaction time is preferablyin the range of 0.5 to 3.0 hours. The reaction is preferably carried outunder stirring.

After the reaction described above is completed, the compoundrepresented by the formula (II) is obtained by pouring the reactionmixture resulting from the reaction into ice water, extracting theresultant mixture with an organic solvent such as ethyl acetate,chloroform and benzene, separating an organic layer from the mixture,washing the organic layer with water, drying the washed organic layer,evaporating the dry organic layer under a reduced pressure, andpurifying the resultant residue. This purification can be effected bymeans of silica gel column chromatography, for example.

As examples of the diluent which is used in producing the cyclopentanonederivative represented by the formula (II) from the compound of theformula (VII) and the compound of the formula (VI), there can be citedhydrocarbons such as benzene, toluene, xylene and hexane; halogenatedhydrocarbons such as methylene chloride, chloroform and carbontetrachloride; ethers such as diethyl ether, diisopropyl ether andtetrahydrofuran; and acetonitrile, dimethyl formamide, and dimethylsulfoxide.

The production of the compound represented by the formula (II) describedabove is effected, for example, by dissolving a compound represented bythe formula (VI) in a diluent described above and adding to theresultant solution a compound represented by the formula (VII), eitherdirectly or in a state dissolved in the diluent, preferably in an amountin the range of 0.3 to 1.0 equivalent to the compound of (VI), orconversely by dissolving the compound of the formula (VII) in thediluent and adding to the resultant solution a solution of the compoundrepresented by the formula (VI) in a diluent.

Though this reaction can be carried out at any desired temperaturebetween the freezing point and the boiling point of the diluent used asa solvent, it is practically preferable to be carried out at atemperature in the range of 0° to 150° C. The reaction time ispreferably in the range of 0.5 to 3.0 hours. The reaction is preferablycarried out under stirring.

After the reaction described above is completed, the compoundrepresented by the formula (IV) is obtained by pouring the reactionmixture resulting from the reaction into ice water, extracting theresultant mixture with an organic solvent such as ethyl acetate,chloroform and benzene, separating an organic layer from the mixture,washing the organic layer with water, drying the washed organic layer,evaporating the dry organic layer under a reduced pressure, andpurifying the resultant residue. This purification can be effected bymeans of silica gel column chromatography, for example.

As examples of the diluent which is used in producing the cyclopentanonederivative represented by the formula (II) from the compound of theformula (IV), there can be cited hydrocarbons such as benzene, toluene,xylene and hexane; alcohols such as methanol and ethanol; ethers such asdiethyl ether, diisopropyl ether and tetrahydrofuran; and acetonitrile,dimethylformamide, and dimethyl sulfoxide. The use of such a diluent asdescribed above is not always required herein.

In the production described above, the reaction is occasionally carriedout in the presence of an acid in the presence or absence of theaforementioned diluent. As examples of the acid thus used in thereaction, there can be cited inorganic acids such as hydrochloric acid,hydrobromic acid, hydroiodic acid and sulfuric acid, and organic acidssuch as acetic acid, tartaric acid and benzoic acid.

The production described above is carried out by adding an acidexemplified above to an intermediate represented by the formula (IV)optionally dissolved in the aforementioned diluent.

Though the reaction can be carried out at a desired temperature in therange of the freezing point and the boiling point of the aforementioneddiluent as a solvent or the acid, it is practically preferable to becarried out at a temperature in the range of 0° to 150° C. The reactiontime is preferably in the range of 0.5 to 3 hours. This reaction ispreferably carried out under stirring.

After the reaction described above is completed, the compoundrepresented by the formula (II) is obtained by pouring the reactionmixture resulting from the reaction into ice water, extracting theresultant mixture with an organic solvent such as ethyl acetate,chloroform and benzene, separating an organic layer from the mixture,washing the organic layer with water, drying the washed organic layer,evaporating the dry organic layer under a reduced pressure, andpurifying the resultant residue. This purification can be effected bymeans of silica gel column chromatography, for example.

Now, the usefulness of the azole derivatives of the present inventionrepresented by the formula (I) as an active ingredient ofagricultural/horticultural fungicide will be described below.

The azole derivatives according to the present invention are effectivein preventing and curing the broad spectrum of plant diseases such as,

Pseudope-ronospora cubensis of cucumber, Pyricularia oryzae of rice,Cochliobolus miyabeanus of rice, Xanthomonas oryzae of rice, Rhizoctoniasolani of rice, Helminthosporium sigmoideum of rice, Gibberellafujikuroi of rice, Podosphaera leucotricha of apple, Venturia inaequalisof apple, Sclerotinia mali of apple, Alternaria mali of apple, Valsamali of apple, Alternaria kikuchiana of pear, Phllllactinia pyri ofpear, Venturia nashicola of pear, Uncinula necator of grape, Phakosporaampelopsidis of grape, Erysiphe graminis f. sp. hordei of barley,Rhynchosporium secalis of barley, Puccinia graminis of barley, Pucciniatriformis of barley, Puccinia recondita of wheat, Septoria tritici ofwheat, Puccinia triformis of wheat, Erysiphe graminis f. sp. tritici ofwheat, Sphaerotheca fuliginea of melon, Fusariumoxysporum of watermelon, Erysiphe cichoracearum of tomato, Alternaria solani of tomato,Erysiphe cichoracearum of eggplant, Sephaerotheca humuli of strawberry,Erysiphe cichoracearum of tobacco, Alternaria longipes of tobacco,Sclerotinia cinerea of peach, Fusarium oxysporum f. cucumerinum ofcucumber, Fusarium oxysporum f. raphani of radish, Colletotrichumlagenarium of melons, Cercospora beticola of beet, Alternaria solani ofpotato, Septoria glycines of soybean, Cercospora kikuchii of soybean,Sclerotinia cinerea of stone-fruits, Botrytis cinerea and Sclerotiniasclerotiorum of various crops.

The azole derivatives of the present invention shows not merely apreventive effect but also a curative effect on some of theaforementioned plant diseases.

The use of an azole derivative represented by the formula (I) in anagricultural/horticultural fungicide can be attained by formulating thecompound, either directly or as mixed with a carrier or a diluent, inthe form of dust, wettable powder, granules, emulsion, or solution so asto be advantageously used in an intended application. Of course, theaforementioned effect of the fungicide can be further enhanced byallowing the fungicide to incorporate therein such adjuvants asspreader, emulsifier, wetting agent, and fixing agent, when necessary,in addition to the aforementioned carrier.

Incidentally, the azole derivative according to the present inventioncontains a 1,2,4-triazole ring or an imidazole ring and, therefore, canbe used also in the form of an inorganic acid salt, an organic acidsalt, or a metal complex salt.

Further, since the azole derivative according to the present inventionpossesses a substituted phenylalkyl group and an azolylmethyl grouprespectively at the 1st position and the 2nd position of a cyclopentanering, stereoisomers such as geometric isomers and optical isomers exist.The present invention includes all the independent isomers and mixturesof varying isomers in desired ratios. The agricultural/horticulturalfungicides according to the present invention, therefore, include thosefungicides containing as an active ingredient these isomers eitherindependently or in the form of mixtures.

Now, typical processes adopted for the production of azole derivativesand cyclopentanone derivatives as intermediate therefor and typicalagricultural/horticultural fungicides using such azole derivatives as anactive ingredient will be explained below for the purpose ofdemonstrating the effect of the present invention. It should be noted,however, that the present invention is not limited to the workingexamples below.

EXAMPLE 1 Production of1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-ylmethyl)-cyclopentan-1-ol(Compound No. 1 in Table 1)

A Grignard reagent (4-chlorophenylmagnesium bromide) was prepared bysuspending 0.22 g (9.1 mmol) of magnesium powder in 20 ml of anhydrousdiethyl ether and after adding 0.1 g of 4-bromo-1-chlorobenzene and atrace amount of I₂ thereto, the mixture was refluxed The Grignardreagent was further subjected to 10 minutes' reflux after slowly addinga solution of 1.64 g (8.6 mmol) of 4-bromo-1chlorobenzene in 5 ml ofanhydrous diethyl ether. The resultant reaction mixture was cooled overan ice-water bath. Then, a solution of 1.0 g (6.0 mmol) of2-(1H-1,2,4-triazol1-ylmethyl)cyclopentanone in 5 ml of anhydrousdiethyl ether was added dropwise to the cooled reaction mixture. Themixture consequently formed was removed from the ice-water bath andstirred at room temperature for 30 minutes. The resultant solution,after adding 1N HCl thereto, was extracted with ethyl acetate. The ethylacetate layer was separated, washed with saturated sodium chloridesolution, and dried over anhydrous sodium sulfate. The dried solutionwas then evaporated under a reduced pressure. The residue of theevaporation was purified by silica gel column chromatography (eluate -20 : 1 mixture of chloroform and methanol). Consequently, 150 mg of anoily compound No. 1 was obtained (9% yield).

This compound No. 1 was found by test to possess the followingproperties. The NMR spectrum was measured with TMS as the internalstandard and reported with the following symbols (the same applicable tothe following examples).

s: Singlet

d: Doublet

m: Multiplet

b: Broad line

(1) IR (film method) :ν_(max) 300, 2950, 1480, 1270, 1140 cm⁻¹

(2) NMR (CDCl₃, ppm): δ1.43-3.00 (m, 7H),

3.43 (bs, 1H), 4.13 (d, 2H, J=7Hz)

7.27 (s, 4H), 7.67 (s, 1H),

7.80 (s, 1H)

EXAMPLE 2 Production of1-(4-chlorobenzyl)-2-(lH-1,2,4-triazol-1-ylmethyl)cyclopentan-1-ol(Compound No. 2 of Table 1)

In a solution of 3.8680 g of 4-chlorobenzyl chloride in 25.1 ml ofanhydrous diethyl ether, 0.555 g of magnesium powder and a catalyticamount of iodide were added and stirred at room temperature untilgeneration of foam ceased. The resultant solution, after adding dropwisea solution of 2.5130 g of 2-(lH-1,2,4-triazol-1-ylmethyl)cyclopentanonein 12.6 ml of anhydrous diethyl ether, was stirred at room temperaturefor 30 minutes.

The reaction mixture consequently obtained was added with 1N HCl andextracted with chloroform to obtain an organic layer. This organic layerwas washed with water, dried over anhydrous sodium sulfate, andevaporated under a reduced pressure.

The residue of the evaporation was purified by silica gel columnchromatography (eluate - ethyl acetate), to obtain 1.1079 g of acompound No. 2.

This compound No. 2 was found to possess the following properties.

(1) Melting point: 127° to 130° C.

(2) IR (KBr method): ν_(max) 3300, 2950, 2910, 1520, 1490, 1420, 1280,1140, 1090, 1010, 500cm⁻¹

(3) NMR (CDCl₃, ppm): δ1.10-2.00 (m, 7H), 2.23 (s, 1H, OH), 2.58 (s,2H), 4.14 (dd, 1H, J =14.0Hz, 6.6Hz), 4.48 (dd, 1H, J =14.0Hz, 6.6Hz),7.03-7.50 (m, 4H), 7.98 (s, 1H), 8.13 (s, 1H).

EXAMPLE 3 Production of1-(4-chlorobenzyl)-2-(1H-imidazol-1-ylmethyl)-cyclopentan-1-ol (CompoundNo. 3 of Table 1)

In a solution of 6.0597 g of 4-chlorobenzyl chloride in 19.6 ml ofanhydrous diethyl ether, 0.8530g of magnesium powder and a catalyticamount of iodine were added and stirred at room temperature untilgeneration of foam ceased. The resultant solution, after adding dropwisea solution of 1.9568 g of 2-(1H-imidazol-1-ylmethyl)cyclopentanone in9.8 ml of anydrous diethyl ether, was stirred at room temperature for 30minutes.

The resultant reaction mixture was added with 1N HCl and extracted withchloroform to obtain an organic layer. This organic layer was washedwith water, dried over anhydrous sodium sulfate, and evaporated under areduced pressure.

The residue of the evaporation was purified by silica gel columnchromatography (eluate - 15:1 mixture of chloroform and methanol) toobtain 1.5027 g of a compound No. 3, and which was recrystallized fromethyl acetate to afford 1.2059 g of pure compound No. 3.

This compound was found to possess the following properties.

(1) Melting point: 152° to 153° C.

(2) IR (KBr method): ν_(max) 3125, 2950, 1490, 1230, 1110, 1090, 1080,730, 660 cm⁻¹

(3) NMR (CDCl₃, ppm): δ1.27-2.17 (m, 7H), 2.27 (s, 1H, 0H), 2.63 (s,2H), 3.85 (dd, 1H, J=14.0Hz, 6.6Hz), 4.20 (dd, 1H, J=14.0Hz, 6.6Hz),6.93 (d, 1H, J=1.6Hz), 7.03 (d-like, 1H), 7.13-7.43 (m, 4H), 7.47 (bs,1H).

EXAMPLE 4 Production of 2-(1H-imimdazol-1-ylmethyl)cyclopentanoneethyleneketal (IV)

After washing 1.0319 g of 60% NaH with anhydrous benzene, 23.7 ml ofanhydrous dimethyl formamide was added thereto. Subsequently after mixedwith 1.7563 g of imidazole, the mixture was stirred at room temperatureuntil generation of foam ceased. The resultant reaction mixture wasadded dropwise with a solution of 4.7357 g of2-methanesulfonyloxymethylcyclopentanone ethyleneketal (VII) in 9.5 mlof anhydrous dimethyl formamide at room temperature, and stirred over anoil bath at 90° C. for 1 hour to complete the reaction. The reactionsolution was poured into ice water and extracted with methylenechloride, to obtain an organic layer. This organic layer was washed withwater, dried over anhydrous sodium sulfate, and evaporated under areduced pressure.

The residue of the evaporation was purified by silica gel columnchromatography (eluate - ethyl acetate), to obtain 3.6593 g of an oilycompound indicated in the caption.

This compound was found to possess the following properties.

(1) IR (film method): ν_(max) 2960, 2880, 1510, 1230, 1025, 665 cm⁻¹

(2) NMR (CDCl₃, ppm): δ1.05-2.05 (m, 6H), 2.05-2.75 (m, 1H), 3.81 (dd,1H, J =14.0Hz, 6.2Hz), 3.83 (d-like, 4H, J=1.4Hz), 4.15 (dd, 1H,J=14.0Hz, 6.2Hz), 6.94 (d-like, 1H), 7.04 (s-like, 1H), 7.48(bs, 1H).

EXAMPLE 5 Production of 2-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanoneethyleneketal (IV)

After washing 0.6475 g of 60% NaH with anhydrous benzene, 14.9 ml ofanhydrous dimethyl formamide was added thereto. Subsequently after mixedwith 1.1181 g of 1,2,4-triazole, the mixture was stirred at roomtemperature until generation of foam ceased. Into the resultant reactionmixture, solution of 2.9715 g of2-methanesulfonyloxymethylcyclopentanone ethyleneketal (VII) in 6.0 mlof anhydrous dimethyl formamide were added at room temperature, andstirred over an oil bath at 90° C for 1 hour to complete the reaction.The reaction solution was poured into ice water and extracted withmethylene chloride to obtain an organic layer. This organic layer waswashed with water, dried over anhydrous sodium sulfate, and evaporatedunder a reduced pressure.

The residue of the evaporation was purified by silica gel columnchromatography (eluate - ethyl acetate), to obtain 2.1972 g of an oilycompound indicated in the caption.

The compound was found to possess the following properties.

(1) IR (film method): v_(max) 2960, 2880, 1510, 1280, 1210, 1140, 1025,680 cm⁻¹

(2) NMR (CDCl₃, ppm): δ1.13-2.13 (m, 6H), 2.29-2.82 (m, 1H), 3.49-3.96(m, 4H). 3.98 (dd, 1H, J =13.6Hz, J=6.2Hz), 4.31 (dd, 1H, J =13.6Hz,J=6.2Hz), 7.79 (s, 1H), 7.99 (s, 1H).

EXAMPLE 6 Production of 2-(lH-imidazol-1-ylmethyl)cyclopentanone (II)

In an oil bath, 3.5603 g of 2-(lH-imidazol-1-ylmethyl)cyclopentanoneethyleneketal (IV) and 17.8 ml of 2N hydrochloric acid added theretowere stirred at 60° C. for 5 hours. The resultant reaction solution wasleft cooling. Then, it was neutralized with an aqueous 1N potassiumhydroxide solution and extracted with methylene chloride, to obtain anorganic layer. This organic layer was washed with water, dried overanhydrous sodium sulfate, and evaporated under a reduced pressure.

The residue of the evaporation was purified by silica gel columnchromatography (eluate - ethyl acetate), to obtain 2.5451 g of an oilycompound indicated in the caption.

This compound was found to possess the following properties.

(1) Refractive index: 1.4947 (22.0° C.)

(2) IR (film method): v_(max) 2970, 1740, 1500, 1240, 1160, 1080 cm⁻¹

(3) NMR (CDCl₃, ppm) : δ1.07-2.73 (m, 7H), 4.07 (s-like, 1H), 4.15(s-like, 1H), 6.78 (d, 1H, J=1.6Hz), 6.92 (s-like, 1H), 7.33 (bs, 1H).

EXAMPLE 7 Production of 2-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanone(II)

After washing 0.9417 g of 60% NaH with anhydrous benzene,18.9 ml ofanhydrous dimethyl formamide was added thereto. The mixture and 1.6262 gof 1,2,4-triazole added thereto were stirred at room temperature untilgeneration of foam subsided. The resultant mixture and a solution of3.7715 g of 2-methanesulfonyloxymethylcyclopentanone (V) in 7.5 ml ofanhydrous dimethyl formamide added dropwise thereto at room temperaturewere stirred at room temperature for 30 minutes. The reaction solutionconsequently formed was poured into ice water and extracted withmethylene chloride to obtain an organic layer. This organic layer waswashed with water, dried over anhydrous sodium sulfate, and evaporatedunder a reduced pressure. The residue of the evaporation was purified bysilica gel column chromatography (eluate - ethyl acetate) to obtain2.6254 g of an oily compound indicated in the caption.

This compound was found to possess the following properties.

(1) Refractive index: 1.4922 (22.5° C.)

(2) IR (film method): ν_(max) 1740, 1510, 1280, 1140 cm⁻¹

(3) NMR (CDCl₃, ppm): δ1.11-3.01 (m, 7H),

4.20 (dd, 1H, J=14.0Hz, J=5.0Hz),

4.50 (dd, 1H, J=14.0Hz, J=5.6Hz),

7.84 (s, 1H), 8.02 (s, 1H).

Now, examples for demonstrating the effectiveness of the compounds ofthis invention will be cited. The carrier, the diluent, and theadjuvants, the mixing ratio thereof, and the contents of the activeingredient can be varied in wide ranges.

EXAMPLE 8

(Dust)

A composition was prepared by pulverizing and mixing the followingcomponents in the indicated proportions.

    ______________________________________                                        Compound of the present invention                                                                    3 parts by weight                                      (Compound No. 2)                                                              Clay                  40 parts by weight                                      Talc                  57 parts by weight                                      ______________________________________                                    

The composition was used as a dust agent.

EXAMPLE 9

(Wettable powder)

A composition was prepared by pulverizing and mixing the followingcomponents.

    ______________________________________                                        Compound of the present invention                                                                   50 parts by weight                                      (Compound No. 3)                                                              Lignin sulfonate       5 parts by weight                                      Alkylsulfonate         3 parts by weight                                      Diatomaceous earth    42 parts by weight                                      ______________________________________                                    

The composition was diluted suitably with water prior to actual use.

EXAMPLE 10

(Granules)

A composition was prepared by uniformly mixing the following components,kneading the resultant mixture with water, molded in a granular formwith an extrusion pelletizer, and dried to produce granules.

    ______________________________________                                        Compound of the present invention                                                                    5 parts by weight                                      (Compound No. 1)                                                              Bentonite             43 parts by weight                                      Clay                  45 parts by weight                                      Lignin sulfonate       7 parts by weight                                      ______________________________________                                    

EXAMPLE 11

(Emulsion)

An emulsion was prepared by uniformly mixing and emulsifying thefollowing components in the indicated proportions.

    ______________________________________                                        Compound of the present invention                                                                   30 parts by weight                                      (Compound No. 7)                                                              Polyoxyethylene alkylallyl ether                                                                    10 parts by weight                                      Polyoxyethylene sorbitan                                                                             3 parts by weight                                      monolaurate                                                                   Xylene                57 parts by weight                                      ______________________________________                                    

EXAMPLE 12

(Test for control of Pseudoperonospora cubensis of cucumber)

Cucumbers (species Sagami Hampaku) were grown in earthen pots 10 cm indiameter (one plant per pot and three pots per plot of treatment) to thetwo-leaf stage. A wettable powder prepared as described in Example 8 wassuspended in water in an active ingredient concentration of 500 ppm.This suspension was applied to the cucumber leaves at a rate of 5 ml perpot. The wet leaves were air dried. Then, a suspension of spores ofPseudoperonospora cubensis of cucumber collected from disease cucumberleaves was inoculated to the dry cucumber leaves by spraying. Thetreated leaves were left standing in a humid atmosphere at 20° to 22° C.for 24 hours. After this standing, the cucumbers were left standing in agreenhouse. On the 5th to 7th day after the inoculation, the treatedcucumber leaves were examined to determine the degree of infection onthe following scale of evaluation. The control index of the fungicidewas calculated from the following formula.

    ______________________________________                                        (Scale of evaluation)                                                         Degree of                                                                     infection     Degree of disease                                               ______________________________________                                        0             Not infected                                                    0.5           Less than 10% of infected area                                                ratio                                                           1             Not less than 10% and less than                                               20% of infected area ratio                                      2             Not less than 20% and less than                                               40% of infected area ratio                                      3             Not less than 40% and less than                                               60% of infected area ratio                                      4             Not less than 60% and less than                                               80% of infected area ratio                                      5             Not less than 80% of infected                                                 area ratio                                                      ______________________________________                                         ##STR25##                                                                

The results of the test are shown in Table 2.

                  TABLE 2                                                         ______________________________________                                        Compound No.                                                                             Concentration (ppm)                                                                           Control index (%)                                  ______________________________________                                        1          500              0                                                 2          500              0                                                 3          500             10                                                 4          500             85                                                 5          500             80                                                 7          500              0                                                 ______________________________________                                    

Example 13: (Test for control of Puccinia recondita of wheat)

Young wheat seedling (species Norin No. 64) were grown in earthen pots10 cm in diameter (16 plants per pot) to the two-leaf stage. A wettablepowder prepared as described in Example 8 was suspended in water in anactive ingredient concentration of 500 ppm. This suspension was appliedto the wheat seedling at a rate of 5 ml per pot. The wheat leaves wetwith the suspension were air dried. Then, a suspension of spores ofPuccinia recondit-a collected from disease wheat leaves was inoculatedto the dry wheat leaves by spraying. The treated wheat leaves were leftstanding in a humid atmosphere at 20° to 23° C. for 24 hours. After thisstanding, the wheat plants were left standing in a greenhouse of glass.On the 7th to 10th day after the inoculation, the treated wheat leavesof 10 plants were examined to determine the degree of infection on thefollowing scale of evaluation. The control index of the fungicide wascalculated from the following formula using the average degree ofinfection per leaf.

    ______________________________________                                        (Scale of evaluation)                                                         Degree of                                                                     infection     Degree of disease                                               ______________________________________                                        0             Not infected                                                    0.5           Less than 10% of infected area                                                ratio                                                           1             Not less than 10% and less than                                               20% of infected area ratio                                      2             Not less than 20% and less than                                               40% of infected area ratio                                      3             Not less than 40% and less than                                               60% of infected area ratio                                      4             Not less than 60% and less than                                               80% of infected area ratio                                      5             Not less than 80% of infected                                                 area ratio                                                      ______________________________________                                         ##STR26##                                                                

The result of the test are shown in Table 3.

                  TABLE 3                                                         ______________________________________                                        Compound No.                                                                             Concentration (ppm)                                                                           Control index (%)                                  ______________________________________                                        1          500             80                                                 2          500             100                                                3          500             85                                                 4          500             60                                                 5          500             60                                                 7          500             80                                                 ______________________________________                                    

EXAMPLE 14 (Test for control of Erysiphe graminis f. sp. tritici ofwheat)

Young wheat seedlings (species Norin No. 64) were grown in earthen pots10 cm in diameter (16 plants per pot and 3 pots per plot of treatment)to the two-leaf stage. A wettable powder prepared as described inExample 8 was suspended in water in an active ingredient concentrationof 500 ppm. This suspension was applied to the wheat seedlings at a rateof 5 ml per pot. The wheat leaves wet with the suspension were airdried. Then, a suspension of spores of Erysiphe graminis f. sp triticicollected from disease wheat leaves was inoculated to the dry wheatleaves by spraying. The treated wheat leaves were left standing in ahumid atmosphere at 20° to 24° C. for 24 hours. After this standing, thewheat plants were left standing in a greenhouse. On the 9th to 11th dayafter the inoculation, the treated wheat leaves were examined todetermine the degree of infection on the following scale of evaluation.The control index of the fungicide was calculated from the followingformula.

    ______________________________________                                        (Scale of evaluation)                                                         Degree of                                                                     infection     Degree of disease                                               ______________________________________                                        0             Not infected                                                    0.5           Less than 10% of infected area                                                ratio                                                           1             Not less than 10% and less than                                               20% of infected area ratio                                      2             Not less than 20% and less than                                               40% of infected area ratio                                      3             Not less than 40% and less than                                               60% of infected area ratio                                      4             Not less than 60% and less than                                               80% of infected area ratio                                      5             Not less than 80% of infected                                                 area ratio                                                      ______________________________________                                         ##STR27##                                                                

The results of the test are shown in Table 4.

                  TABLE 4                                                         ______________________________________                                        Compound No.                                                                             Concentration (ppm)                                                                           Control index (%)                                  ______________________________________                                        1          500             100                                                2          500             100                                                3          500              95                                                4          500              80                                                5          500              95                                                7          500             100                                                ______________________________________                                    

EXAMPLE 15 (Test for fungicidal ability against various disease germs)

Various azole derivates according to the present invention were testedfor fungicidal ability against various disease germs as follows.

Method of test

Various compounds of the present invention was dissolved in dimethylsulfoxide in a prescribed concentration. In an Erlenmeyer flask havingan inner volume of 100 ml, 0.6 ml of the resultant solution and 60 ml ofa PSA culture medium of about 60° C. were thoroughly mixed. Theresultant mixture was poured into a petri dish and left solidifyingtherein. A plate culture medium in which a test germ had been culturedwas punched out by a cork borer 4 mm in diameter. A disc of plateculture medium was superposed by way of inoculation on a platecontaining the aforementioned solution. The germ was incubated at theoptimum growth temperature thereof for one to three days after theinoculation. The growth of germ was determined by measuring the diameterof colony. The rate of inhibiting hypha growth of the compound wasdetermined by comparing the growth of germ in the plot of treatment withthat in the control plot and by the calculation based on the followingformula using the result of comparison.

    R(%)=(dc-dt)·100/dc

wherein R is the rate of inhibiting hypha growth (%), dc is the diameterof colony on the untreated plate, and dt is the diameter of colony onthe treated plate.

The results were evaluated on the following 5-point scale. They areshown in Table 5.

    ______________________________________                                        (Degree of inhibiting growth)                                                 ______________________________________                                        5        not less than 90% of the rate of inhibiting                                   hypha growth                                                         4        not less than 71% and less than 90% of the                                    rate of inhibiting hypha growth                                      3        not less than 41% and less than 71% of the                                    rate of inhibiting hypha growth                                      2        not less than 21% and less than 41% of the                                    rate of inhibiting hypha growth                                      1        less than 21% of the rate of inhibiting                                       hypha growth                                                         ______________________________________                                    

                                      TABLE 5                                     __________________________________________________________________________          Concentration                                                           Compound                                                                            of compound                                                                            Disease germ used                                              No.   (μg/ml)                                                                             P.o.                                                                             C.m.                                                                             G.f.                                                                             H.s.                                                                             R.s.                                                                             Bo.c.                                                                            S.s.                                                                             F.n.                                                                             F.c.                                                                             F.r.                                                                             C.l.                                                                             C.b.                                                                             S.c.                                                                             V.m.                                                                             A.k.                                                                             A.m.              __________________________________________________________________________    1     100      4  4  5  3  2  5  5  5  5  5  3  4  5  5  3  3                 2     100      5  5  5  4  3  5  5  5  5  5  4  5  5  5  4  3                 3     100      5  5  5  4  3  3  5  5  5  5  4  4  5  5  3  4                 4     100      5  5  5  5  3  5  5  5  5  5  5  5  5  5  4  4                 5     100      5  5  3  4  3  5  5  3  3  3  3  3  5  5  3  3                 6     100      5  5  5  4  3  3  5  5  5  5  4  4  5  5  3  4                 7     100      5  4  3  3  3  4  5  3  3  3  3  4  5  5  2  3                 __________________________________________________________________________      The acronyms used in the table indicate the following germs.                 P.o.: Pyricularia oryzae on rice plant                                        C.m.: Cochliobolus miyabeanus on rice plant                                   G.f.: Gibberella fujikuroi on rice plant                                      H.s.: Helminthosporium sigmoideum on rice plant                               R.s.: Rhizoctonia solani on rice plant                                        Bo.c.: Botrytis cinerea-                                                      S.s.: Sclerotinia sclerotirum-                                                F.n.: Fusarium oxysporum f.niveum on watermelon                               F.c.: Fusarium oxysporum f.cucumerinum on cucumber                            F.r.: Fusarium oxysporum f.raphani on Japanese radish                         C.l.: Colletotrichum lagenarium on melons                                     C.b.: Cercospola beticola on sugar beet                                       S.c.: Sclerotinia cinerea on peach                                            V.m.: Valsa mali on apple                                                     A.m.: Alternaria mali on apple                                                A.k.: Alternaria alternata (kikuchiana) on pear                          

What is claimed is:
 1. A cyclopentanone derivative represented by theformula (II): ##STR28## wherein A represents a nitrogen atom.